CA2054166C - Process for producing brown covering layers on copper - Google Patents
Process for producing brown covering layers on copperInfo
- Publication number
- CA2054166C CA2054166C CA002054166A CA2054166A CA2054166C CA 2054166 C CA2054166 C CA 2054166C CA 002054166 A CA002054166 A CA 002054166A CA 2054166 A CA2054166 A CA 2054166A CA 2054166 C CA2054166 C CA 2054166C
- Authority
- CA
- Canada
- Prior art keywords
- copper
- covering layers
- brown
- aqueous solution
- semifinished product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 12
- 230000008569 process Effects 0.000 title claims description 12
- 239000011265 semifinished product Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000007788 roughening Methods 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims 1
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- 241001311547 Patina Species 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001464 adherent effect Effects 0.000 abstract description 3
- 238000009435 building construction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007688 edging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 241001620634 Roger Species 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/24—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like
- E04D3/30—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like of metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
- Paints Or Removers (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemically Coating (AREA)
- Adornments (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tyre Moulding (AREA)
Abstract
A method for producing a uniform and adherent brown covering layer (brown patina) on surfaces of semifinished products made of copper, particularly on rolled tapes or sheets used in building construction. The surface of the copper semifinished product is first roughened by means of a mechanical treatment. The copper semifinished product is then heat treated at a temperature lying within the temperature range of 150 to 650°C for the duration of 0.1 to 30 minutes.
The copper semifinished product can be advantageously subjected to a chemical postoxidation treatment immediately following the heat treatment.
The copper semifinished product can be advantageously subjected to a chemical postoxidation treatment immediately following the heat treatment.
Description
2C~4~.~6 .~..
PROCESS FOR PRODUCING BROWN COVERING LAYERS ON COPPER
Background of the Invention The invention relates generally to a process for producing brown covering layers on semifinished products made of copper, especially for rolled tapes and sheets used in roofing and facing.
Under normal atmospheric conditions, a very adhesive and resistant covering layer of copper oxide forms on the surface of bare metal copper. This oxide film, which at first is very thin, stabilizes the surface of the copper material with respect to the effects of the atmosphere. Ideally, the slow further development of the oxide layer, which results from the continued chemical reaction of the copper with moisture and atmospheric oxygen, gradually forms a uniform brown coloring (brown patina), so that the surface of the copper increasingly loses its metallic shine. With the passage of time, the brown covering layer becomes progressively darker and turns into an anthracite brown. This is the final state that usually sets in on perpendicular building surfaces, such as on an outer-wall facing. In the case of sloped roof surfaces, the roof layer changes in color by reacting with the substances contained in the atmosphere such as sulphur dioxide, carbon dioxide and chlorides, to form alkaline copper compounds, until the patina-green that is typical of copper is attained.
Under certain atmospheric conditions, however, the formation of the brown covering layer can be considerably delayed and also accelerated in spots, resulting in a relatively long wait until the copper surface becomes uniformly discolored. Deviations from a uniform shade are especially noticeable in the initial weathering stage. First, irregular dark spots and/or stripes form over and over again ~s~:
on the copper surface. As the weathering action continues, however, these color variations noticeably decline due to atmospheric influences.
This invention is directed to the development of a process by which a uniform and very adherent brown covering layer (brown patina) can be produced, if desired on a large scale, on the surface of a semifinished product made of copper. This covering layer will not become damaged or peel off when it is further processed as may be required in building construction.
Summary of the Invention Accordingly, the invention provides a processfor producing brown covering layers on semifinished products made of copper, comprising mechanically roughening the surface of a copper product;
heat treating the copper product in a controlled, oxidizing atmosphere containing about 25% oxygen by volume, at a temperature between 150 to 650°C fox a duration of between 0.1 and 30 minutes;
and immediately following the heat treatment, treating the copper semifinished product with an aqueous solution of a metallic salt selected from the group consisting of potassium chlorate, potassium permanganate, sodium hypochlorite, and mixtures thereof with copper sulphate.
The process according to the invention helps to provide an unexpectedly simple way to successfully achieve a factory pre-weathering (brown patination) of the surface of a semifinished product made of copper, without having to wait for the dark-brown discoloration of the copper surface that is dependent on the long-C
M...
-term action of the atmosphere. This advantage particularly accommodates one's aesthetic feeling for a uniformly colored copper surface, for example for a roofing or facing composed of copper profile elements. A considerable advantage also lies in the fact 2a 'w~.
that when repair work becomes necessary, suitable copper tapes or sheet copper provided with a brown patina can be made available to the plumber or other repairman. Thus, this pre-patinated material makes it possible to add, without any transition, to facings, which have already been exposed for a longer time to the atmospheric influences, without any differences becoming visible with respect to the shade of the brown covering layers on the individual facade elements.
Furthermore, the pre-patinated tapes or sheets of copper manufactured according to the process of the invention have covering layers which show exceptional adhesive or adherent strength and also remain deformation-resistant when subjected to bending or edging;
i . a . , they do not show any separation or cracking. Even f roger marks, which often cannot be avoided when roofing and facings are installed, remain generally inconspicuous on the pre-patinated surface .
One can attain a still better adhesive strength for the covering layer and a particularly more uniform brown coloration of the pre-patinated copper surface by carrying out a chemical postoxidation immediately following the heat treatment, with an aqueous solution of at least one metallic salt from the group which includes potassium chlorate, potassium permanganate and sodium hypochlorite, alone or in a mixture with copper sulphate.
Detailed Description A number of chemical and electrolytic processes are known that give copper surfaces a brown color. However, without previous thermal oxidation, they often lead to an insufficient color saturation of the covering layers, particularly on a large scale.
PROCESS FOR PRODUCING BROWN COVERING LAYERS ON COPPER
Background of the Invention The invention relates generally to a process for producing brown covering layers on semifinished products made of copper, especially for rolled tapes and sheets used in roofing and facing.
Under normal atmospheric conditions, a very adhesive and resistant covering layer of copper oxide forms on the surface of bare metal copper. This oxide film, which at first is very thin, stabilizes the surface of the copper material with respect to the effects of the atmosphere. Ideally, the slow further development of the oxide layer, which results from the continued chemical reaction of the copper with moisture and atmospheric oxygen, gradually forms a uniform brown coloring (brown patina), so that the surface of the copper increasingly loses its metallic shine. With the passage of time, the brown covering layer becomes progressively darker and turns into an anthracite brown. This is the final state that usually sets in on perpendicular building surfaces, such as on an outer-wall facing. In the case of sloped roof surfaces, the roof layer changes in color by reacting with the substances contained in the atmosphere such as sulphur dioxide, carbon dioxide and chlorides, to form alkaline copper compounds, until the patina-green that is typical of copper is attained.
Under certain atmospheric conditions, however, the formation of the brown covering layer can be considerably delayed and also accelerated in spots, resulting in a relatively long wait until the copper surface becomes uniformly discolored. Deviations from a uniform shade are especially noticeable in the initial weathering stage. First, irregular dark spots and/or stripes form over and over again ~s~:
on the copper surface. As the weathering action continues, however, these color variations noticeably decline due to atmospheric influences.
This invention is directed to the development of a process by which a uniform and very adherent brown covering layer (brown patina) can be produced, if desired on a large scale, on the surface of a semifinished product made of copper. This covering layer will not become damaged or peel off when it is further processed as may be required in building construction.
Summary of the Invention Accordingly, the invention provides a processfor producing brown covering layers on semifinished products made of copper, comprising mechanically roughening the surface of a copper product;
heat treating the copper product in a controlled, oxidizing atmosphere containing about 25% oxygen by volume, at a temperature between 150 to 650°C fox a duration of between 0.1 and 30 minutes;
and immediately following the heat treatment, treating the copper semifinished product with an aqueous solution of a metallic salt selected from the group consisting of potassium chlorate, potassium permanganate, sodium hypochlorite, and mixtures thereof with copper sulphate.
The process according to the invention helps to provide an unexpectedly simple way to successfully achieve a factory pre-weathering (brown patination) of the surface of a semifinished product made of copper, without having to wait for the dark-brown discoloration of the copper surface that is dependent on the long-C
M...
-term action of the atmosphere. This advantage particularly accommodates one's aesthetic feeling for a uniformly colored copper surface, for example for a roofing or facing composed of copper profile elements. A considerable advantage also lies in the fact 2a 'w~.
that when repair work becomes necessary, suitable copper tapes or sheet copper provided with a brown patina can be made available to the plumber or other repairman. Thus, this pre-patinated material makes it possible to add, without any transition, to facings, which have already been exposed for a longer time to the atmospheric influences, without any differences becoming visible with respect to the shade of the brown covering layers on the individual facade elements.
Furthermore, the pre-patinated tapes or sheets of copper manufactured according to the process of the invention have covering layers which show exceptional adhesive or adherent strength and also remain deformation-resistant when subjected to bending or edging;
i . a . , they do not show any separation or cracking. Even f roger marks, which often cannot be avoided when roofing and facings are installed, remain generally inconspicuous on the pre-patinated surface .
One can attain a still better adhesive strength for the covering layer and a particularly more uniform brown coloration of the pre-patinated copper surface by carrying out a chemical postoxidation immediately following the heat treatment, with an aqueous solution of at least one metallic salt from the group which includes potassium chlorate, potassium permanganate and sodium hypochlorite, alone or in a mixture with copper sulphate.
Detailed Description A number of chemical and electrolytic processes are known that give copper surfaces a brown color. However, without previous thermal oxidation, they often lead to an insufficient color saturation of the covering layers, particularly on a large scale.
x..:
~"..""""'. '~ d~
Furthermore, spots and streaks cannot normally be prevented from remaining on the surface, particularly when a processing solution is applied through a dipping treatment. The present invention avoids many of these problems.
In one embodiment, a cold-rolled and possibly degreased tape of SF copper, according to DIN 1787, having a thickness of 0.6 mm and a breadth of 1,000 mm, was uniformly roughened with a grinding device. Endless sanding belts having a coarseness no. 180 and no. 320 were used for the surface treatment. The copper tape was then fed for heat treatment to a gas-heated continuous-heating furnace. For the surface oxidation of the copper tape which was heat-processed in a continuous cycle in the temperature range of 150 to 350°C, preferably at about 275°C, a controlled gas atmosphere with an oxygen component of about 25 volume % was provided in the furnace.
The heat treatment interval may vary between 0.1 and 30 minutes.
After a short cooling interval, the pre-oxidized copper tape was then dipped, at a working temperature of about 80°C (a 3a 2~'541~56 ,~",;~nperature in the range of 20C to 90C could be used) , in a bath containing an aqueous solution of a mixture of 50 g/1 potassium chlorate (a concentration in the range of 20 g/1 to 70 g/1 could be used) and 100 g/1 copper sulphate pentahydrate (a concentration in the range of 50 g/1 to 150 g/1 could be used). The duration of exposure to the processing solution amounted to about 2 to 3 minutes (this could vary between 1 and 10 minutes). The copper tape was subsequently rinsed with water and dried with hot air. After these treatment steps, the copper tape showed a very uniform covering layer with an intensive, dark-brown coloring. The brown patina proved to be very abrasion-proof. After additional bending and edging operations, the covering layer did not show any evidence of damage or separation.
~"..""""'. '~ d~
Furthermore, spots and streaks cannot normally be prevented from remaining on the surface, particularly when a processing solution is applied through a dipping treatment. The present invention avoids many of these problems.
In one embodiment, a cold-rolled and possibly degreased tape of SF copper, according to DIN 1787, having a thickness of 0.6 mm and a breadth of 1,000 mm, was uniformly roughened with a grinding device. Endless sanding belts having a coarseness no. 180 and no. 320 were used for the surface treatment. The copper tape was then fed for heat treatment to a gas-heated continuous-heating furnace. For the surface oxidation of the copper tape which was heat-processed in a continuous cycle in the temperature range of 150 to 350°C, preferably at about 275°C, a controlled gas atmosphere with an oxygen component of about 25 volume % was provided in the furnace.
The heat treatment interval may vary between 0.1 and 30 minutes.
After a short cooling interval, the pre-oxidized copper tape was then dipped, at a working temperature of about 80°C (a 3a 2~'541~56 ,~",;~nperature in the range of 20C to 90C could be used) , in a bath containing an aqueous solution of a mixture of 50 g/1 potassium chlorate (a concentration in the range of 20 g/1 to 70 g/1 could be used) and 100 g/1 copper sulphate pentahydrate (a concentration in the range of 50 g/1 to 150 g/1 could be used). The duration of exposure to the processing solution amounted to about 2 to 3 minutes (this could vary between 1 and 10 minutes). The copper tape was subsequently rinsed with water and dried with hot air. After these treatment steps, the copper tape showed a very uniform covering layer with an intensive, dark-brown coloring. The brown patina proved to be very abrasion-proof. After additional bending and edging operations, the covering layer did not show any evidence of damage or separation.
Claims (5)
1. A process for producing brown covering layers on semifinished products made of copper, comprising:
mechanically roughening the surface of a copper product;
heat treating the copper product in a controlled, oxidizing atmosphere containing about 25% oxygen by volume, at a temperature between 150 to 650°C for a duration of between 0.1 and 30 minutes;
and immediately following the heat treatment, treating the copper semifinished product with an aqueous solution of a metallic salt selected from the group consisting of potassium chlorate, potassium permanganate, sodium hypochlorite, and mixtures thereof with copper sulphate.
mechanically roughening the surface of a copper product;
heat treating the copper product in a controlled, oxidizing atmosphere containing about 25% oxygen by volume, at a temperature between 150 to 650°C for a duration of between 0.1 and 30 minutes;
and immediately following the heat treatment, treating the copper semifinished product with an aqueous solution of a metallic salt selected from the group consisting of potassium chlorate, potassium permanganate, sodium hypochlorite, and mixtures thereof with copper sulphate.
2. The process for producing brown covering layers according to claim 1, wherein the mechanical treatment is carried out through grinding or brushing.
3. The process for producing brown covering layers according to claim 1 or 2, wherein an aqueous solution of 20 to 70 g/l potassium chlorate and 50 to 150 g/l copper sulphate pentahydrate is applied to the surface of the copper semifinished product.
4. The process for producing brown covering layers according to claim 1, 2 or 3, wherein the copper semifinished product is dipped in the aqueous solution at a temperature lying within the temperature range of 20 to 90°C for a duration of from 1 to 10 minutes.
5. The process for providing brown covering layers according to claim 1, 2 or 3, wherein the aqueous solution includes copper sulfate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4034249.2 | 1990-10-27 | ||
| DE4034249A DE4034249A1 (en) | 1990-10-27 | 1990-10-27 | METHOD FOR PRODUCING BROWN COVER LAYERS ON COPPER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2054166A1 CA2054166A1 (en) | 1992-04-28 |
| CA2054166C true CA2054166C (en) | 1999-08-17 |
Family
ID=6417188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002054166A Expired - Fee Related CA2054166C (en) | 1990-10-27 | 1991-10-24 | Process for producing brown covering layers on copper |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5282890A (en) |
| EP (1) | EP0483568B1 (en) |
| JP (1) | JP3111094B2 (en) |
| AT (1) | ATE128192T1 (en) |
| AU (1) | AU633764B2 (en) |
| CA (1) | CA2054166C (en) |
| DE (2) | DE4034249A1 (en) |
| DK (1) | DK0483568T3 (en) |
| ES (1) | ES2077133T3 (en) |
| FI (1) | FI96777C (en) |
| GR (1) | GR3018053T3 (en) |
| NO (1) | NO303787B1 (en) |
| PT (1) | PT99330B (en) |
| RU (1) | RU2023750C1 (en) |
| ZA (1) | ZA917973B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2069501B1 (en) * | 1993-10-11 | 1996-02-16 | Collado Manuel Torrejon | COPPER AGING PROCEDURE. |
| DE4404699A1 (en) * | 1994-02-15 | 1995-08-17 | Kabelmetal Ag | Process for the production of tinned strips or sheets made of copper or a copper alloy |
| DE19542410A1 (en) * | 1994-11-14 | 1996-05-15 | Furukawa Electric Co Ltd | Building material quickly forming natural patina |
| DE19523646A1 (en) * | 1995-06-29 | 1997-01-02 | Km Europa Metal Ag | Copper tape or sheet with a brown top layer and process for its manufacture |
| US6086743A (en) * | 1997-08-06 | 2000-07-11 | Gould Electronics, Inc. | Adhesion enhancement for metal foil |
| DE19809904A1 (en) * | 1998-03-07 | 1999-09-09 | Km Europa Metal Ag | Process and reaction solution to create a patina |
| DE102004036082A1 (en) * | 2004-07-24 | 2006-02-09 | Km Europa Metal Ag | Method for producing an inorganic covering layer on the surface of a product and panel or band-shaped product |
| US8057587B2 (en) | 2008-05-12 | 2011-11-15 | Michael Beeck | Composition for coloring solder |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1319508A (en) * | 1919-10-21 | Gotjgh | ||
| DE625298C (en) * | 1934-05-03 | 1936-02-06 | Metallwerke A G Dornach | Process for browning copper and copper alloys, especially brass |
| JPS589831B2 (en) * | 1976-03-29 | 1983-02-23 | 古河電気工業株式会社 | Copper blackening treatment method |
| DE3108160C2 (en) * | 1981-02-06 | 1984-12-06 | M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München | Process for the production of oxide layers on chrome and / or nickel alloy steels |
| JPS60159174A (en) * | 1984-01-27 | 1985-08-20 | Daikan:Kk | Manufacture of copper plate for roof having artificial patina |
| JPS634053A (en) * | 1986-06-24 | 1988-01-09 | Susumu Ishikawa | Method for forming patina film on surface of copper product or the like |
| US4954185A (en) * | 1987-01-14 | 1990-09-04 | Kollmorgen Corporation | Method of applying adherent coating on copper |
| JP2662013B2 (en) * | 1989-02-07 | 1997-10-08 | 古河電気工業株式会社 | Roofing material of Cu or Cu alloy |
-
1990
- 1990-10-27 DE DE4034249A patent/DE4034249A1/en not_active Withdrawn
-
1991
- 1991-10-04 ZA ZA917973A patent/ZA917973B/en unknown
- 1991-10-11 ES ES91117338T patent/ES2077133T3/en not_active Expired - Lifetime
- 1991-10-11 AT AT91117338T patent/ATE128192T1/en not_active IP Right Cessation
- 1991-10-11 EP EP91117338A patent/EP0483568B1/en not_active Expired - Lifetime
- 1991-10-11 DK DK91117338.3T patent/DK0483568T3/en active
- 1991-10-11 DE DE59106523T patent/DE59106523D1/en not_active Expired - Lifetime
- 1991-10-15 FI FI914862A patent/FI96777C/en active
- 1991-10-16 RU SU915001722A patent/RU2023750C1/en not_active IP Right Cessation
- 1991-10-24 CA CA002054166A patent/CA2054166C/en not_active Expired - Fee Related
- 1991-10-25 JP JP03280070A patent/JP3111094B2/en not_active Expired - Fee Related
- 1991-10-25 NO NO914196A patent/NO303787B1/en unknown
- 1991-10-25 AU AU86776/91A patent/AU633764B2/en not_active Ceased
- 1991-10-25 PT PT99330A patent/PT99330B/en not_active IP Right Cessation
- 1991-10-28 US US07/783,002 patent/US5282890A/en not_active Expired - Lifetime
-
1995
- 1995-11-09 GR GR950403151T patent/GR3018053T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2077133T3 (en) | 1995-11-16 |
| DE59106523D1 (en) | 1995-10-26 |
| FI914862A0 (en) | 1991-10-15 |
| NO914196D0 (en) | 1991-10-25 |
| EP0483568A1 (en) | 1992-05-06 |
| JP3111094B2 (en) | 2000-11-20 |
| CA2054166A1 (en) | 1992-04-28 |
| PT99330B (en) | 1999-02-26 |
| FI96777C (en) | 1996-08-26 |
| DE4034249A1 (en) | 1992-04-30 |
| RU2023750C1 (en) | 1994-11-30 |
| PT99330A (en) | 1992-09-30 |
| ATE128192T1 (en) | 1995-10-15 |
| AU8677691A (en) | 1992-04-30 |
| EP0483568B1 (en) | 1995-09-20 |
| JPH05339701A (en) | 1993-12-21 |
| GR3018053T3 (en) | 1996-02-29 |
| NO914196L (en) | 1992-04-28 |
| NO303787B1 (en) | 1998-08-31 |
| AU633764B2 (en) | 1993-02-04 |
| FI96777B (en) | 1996-05-15 |
| US5282890A (en) | 1994-02-01 |
| ZA917973B (en) | 1992-06-24 |
| DK0483568T3 (en) | 1996-01-02 |
| FI914862A (en) | 1992-04-28 |
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